200908785 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種有機電激發光元件之基板的預處理 方法，較具體而言，係關於在基板上形成金屬氧化物之透 明電極之基板的預處理方法。 近來一種自身發光型之發光元件的有機EL元件（有機 電激發光元件）受到注意。在用於製造有機電激發光元件的 基本方法中，在基板上形成由IT 0 (銦-錫氧化物）所製成之 透明電極的陽極圖案，並積層有機電激發光層與陰極於該 基板上。該有機電激發光元件容易受到濕氣或氧氣的有害 影響。因此，若濕氣或雜質聚集於形成陽極圖案之基板上， 所製造之有機電激發光元件可能具有一個稱爲暗點（或暗 區）之不發光的區域（無發光區域），或者可能具有亮度不 均。因此，需要執行該基板之預處理。 【先前技術】 基板之預處理包括用於從基板除去導致暗點之濕氣的 處理。已提出一種基板的預處理方法，其中藉由加熱除去 濕氣並防止濕氣再度聚集於基板上。例如，日本公開專利 第2005 - 1 9082 2號揭示一種安置有機電激發光元件於基板 上之濕氣除去方法。該有機電激發光元件具有第一電極、 絕緣層、至少包括一發光層之有機層、與第二電極，並依 序積層彼等。該方法包括至少在形成絕緣層後加熱基板以 從基板除去濕氣的步驟，和在濕氣除去處理後在維持大氣 於低露點之下降低基板溫度。上述發表揭示降低基板溫度 200908785 同時釋出環境中之氣體並導入具有低露點之新氣體於該環 境中或吹送具有低露點之新氣體至基板。 然而，揭示於上述發表中之基板的預處理方法的目的 受限於基板上濕氣之除去。 本發明者等已揭示當藉由僅導入具有低露點之氣態氮 氣於處理室而執行用於基板之加熱處理，作爲形成金屬氧 化物之透明電極於基板上的預處理時，可能劣化形成於基 板之有機電激發光元件的性能（例如，亮度不均）。具體而 言，本發明者等發現用於加熱處理之環境氣體對於由金屬 氧化物所製成之透明電極的性能有不利的影響。亦發現可 能因其他條件而劣化所製造之有機電激發光元件的性能。 【發明內容】 本發明之一目的係提供一種基板之預處理方法，其中 除去基板上的濕氣，以及當製造有機電激發光元件時，在 濕氣除去之同時，執行用於形成於該基板上之由金屬氧化 物所製成之透明電極的適當表面處理。 爲了達成上述目的，本發明之一態樣提供一種基板的 預處理方法。形成由金屬氧化物所製成的透明電極於基板 上’並在預處理後將形成有機電激發光元件之複數層積層 於透明電極上。該預處理方法包括：將具有透明電極之基 板收納於提供有加熱器之處理室中；加熱基板同時導入氧 氣和惰性氣體的混合氣體於處理室中以取代處理室中的氣 體’以及S又疋混合氣體進入處理室之導入速度，使得混合 氣體以每分鐘處理室之全部體積之1/60以上與1/15以下 200908785 的量導入於處理室中。 本發明之另一態樣係提供一種用於有機電激發光元件 的製造方法，其中包括：形成由金屬氧化物所製成的透明 電極於基板上；將具有透明電極之基板收納於提供有加熱 器之處理室中；加熱基板同時將氧氣和惰性氣體之混合氣 體導入於處理室中以取代處理室中的氣體；設定混合氣體 進入處理室之導入速度’使得混合氣體以每分鐘處理室之 全部體積之1/60以上與1/15以下的量導入於處理室中； 冷卻基板至室溫；以及將形成有機電激發光元件之複數層 積層於透明電極上。 根據本發明，不僅除去聚集於基板與透明電極上之濕 氣，而且同時執行由金屬氧化物所製成之透明電極之表面 重組（reforming)。”透明電極之表面重組”係表示一種處 理，其中藉由使用已執行表面處理之基板所製造之有機電 激發光元件的性能，滿足預定之條件。有機電激發光元件 之性能包括例如初始特性、壽命、亮度不均、與暗點的發 生。通常，用於加熱乾燥處理的氣體僅作用爲傳送藉由加 熱所蒸發之濕氣至外部的擴帶氣體（carrier gas)。根據本發 明之混合氣體作用爲傳送所蒸發之濕氣的攜帶氣體，亦作 用爲防止因濕氣之去除導致由金屬氧化物所製成之透明電 極的表面條件劣化。換言之’混合氣體中所含有之氧氣與 由金屬氧化物所製成之透明電極表面上的金屬氧化物反 應，並重組透明電極之表面條件。 本發明之其他態樣與優點將由下述結合附加圖式、並 200908785 由實例之方式說明本發明之原理而變得明白。 本發明係藉由參考本發明之目前較佳之具體實施例的 以下說明，與以下附加圖式一起，最佳地了解本發明、和 其目的與優點一起。 【實施方式】 將參考第1A與1B圖解釋本發明之一具體實施例。第 1A圖不意地顯示形成有機電激發光元件製造裝置之複數 區塊之第一區塊。 在顯示於第1A圖之第一區塊中實施各種不同的前處 理。第一區塊具有一輸送室11與經由輸送室11彼此連接 之複數個處理室1 4至1 7。第一區塊具有連接於沉積有機 電激發光層與電極之第二區塊（無圖示）的傳遞室12。輸送 室Π具有包含具有輸送手臂丨8之機械人的輸送機構13。 輸送機構13經由輸送室11輸送基板至每一個處理室14至 17。輸送室11、傳遞室12、與每一個處理室14至17係連 接於一個抽氣裝置（無圖示），以便藉由抽氣而使其獨立地 抽真空，及在以抽氣抽真空後藉由惰性氣體之導入而使其 在大氣壓下。 處理室包括圍繞著輸送室11而連接於輸送室11的反 轉室14、烘烤室15、UV處理室16與冷卻室17。在反轉 室1 4中，將在基板上形成透明電極圖案之基板予以反轉。 從移轉設備（無圖不）輸送基板至反轉室14。在供烤室15 中’將包含於基板中之濕氣與其他氣體除去並重組透明電 極。烘烤室1 5維持烘烤室i 5之內部於真空狀態並導入預 200908785 定氣體於烘烤室15中。因而，可在預定之環境中進行基板 的烘烤處理（加熱處理）。在UV處理室1 6中執行UV處理 以除去聚集於形成於基板上之透明電極表面上的有機物質 或灰塵。在冷卻室1 7中執行對於基板的冷卻處理。在降低 已於烘烤室15中執行加熱處理之基板的溫度至預定溫度 後’冷卻基板以在冷卻室1 7中藉由冷卻處理而在短時間內 具有室溫。 連接於第一區塊之第二區塊具有遮罩貯存室與複數個 / 沉積室（薄膜形成室）。經由傳遞室1 2轉移在第一區塊中執 \ 行前處理之基板至第二區塊。在第二區塊的每一個沉積室 中，形成有機電激發光元件之複數層，如有機電激發光層 與陰極層，係形成於基板上之透明電極上。 如第1B圖所示，在烘烤室15中定義一卡匣收納室19 並提供基板卡匣2 1於卡匣收納室1 9中。基板卡匣2 1水平 地支撐複數片基板P並能夠被抬升機構2 0提起或降下。提 供乾熱風扇（sirocco fan)23於烘烤室1 5的上半部。形成複 數狹縫24a於位於乾熱風扇23之下之卡匣收納室1 9的分 — 隔壁24上。以HEP A(高效率微粒子空氣）過濾器25覆蓋狹 縫24a。在卡匣收納室19之下半部中形成空氣釋放口 26。 由烘烤室1 5之外部所提供之混合氣體供應部分（無圖 示），經由導管27將氧氣與惰性氣體之混合氣體導入於形 成於乾熱風扇23之轉軸的導入部分。該乾熱風扇23吹送 所導入之混合氣體至在分隔壁24上所提供之HEPA過濾器 2 5。即，乾熱風扇2 3以預定之導入速度將混合氣體導入於 烘烤室15中。藉由乾熱風扇23吹送至HEPA過濾器25之 200908785 混合氣體通過收納著複數片基板P之基板卡匣21’及通過 在烘烤室15之上半部分所提供之加熱器22，並藉由乾熱 風扇23再次吹送至HEPA過濾器25。換言之’藉由乾熱風 扇23所吹送之混合氣體以預定之流速循環於烘烤室1 5 中。循環於烘烤室1 5中之混合氣體的流速相等於混合氣體 之導入速度。 加熱器22能夠加熱基板P高達25〇°C。乾熱風扇23 能夠調整混合氣體進入烘烤室1 5之導入速度，以致於所導 入之混合氣體的流速在0至25 0 L/min的範圍中改變。 將說明以上述所建構之製造裝置的有機電激發光元件 (面板）製造方法。形成IT 0 (銦-錫氧化物）圖案作爲透明電 極於基板上的基板P，係使用不同於示於第1A與1B圖之 製造裝置的裝置所製備。藉由轉移裝置（無圖示）轉移基板P 至製造裝置之反轉室14。在第二區塊之每個沉積室中藉由 向上沉積以沉積薄膜於基板P上。因此，在反轉室1 4中將 基板P反轉使得具有透明電極的表面朝下。因而，在輸送 室Η中輸送手臂18之挾持部分可挾持具有形成基板P表 面之薄膜的透明電極表面。基板Ρ係從UV處理室1 6經由 烘烤室15而輸送至冷卻室17，並以藉由輸送手臂18之挾 持部分挾持基板的狀態予以處理。因而，執行預處理。 藉由運輸手臂1 8，經由傳遞室1 2將用於執行預處理 之基板Ρ運輸至第一區塊。在第_•區塊中，積層每一形成 有機電激發光元件之層於基板ρ上。 將詳細說明其爲預處理之一處理的烘烤處理。 -10- 200908785 使在反轉室14中被反轉的基板P在UV處理室16中 進行UV處理，然後在烘烤室1 5中進行烘烤處理。以使基 板P收納於基板卡匣2 1中的狀態下同時使複數片基板p進 行烘烤處理。在烘烤處理中’從外部導入在大氣壓下露點 爲-30 °C以下之氧氣與在大氣壓下露點爲-30 °c以下之氮氣 的混合氣體於烘烤室1 5 ’而由空氣釋放口 2 6釋放部分混 合氣體至外部。在該狀態下’使加熱器2 2加熱至預定溫度 並在大氣壓力下執行烘烤處理一段預定時間。藉由乾熱風 扇23之啓動調整混合氣體的導入速度（流速）。 在所使用之混合氣體中的氧氣與惰性氣體比例（氧 氣：惰性氣體）係在體積比1 . 8 : 8.2至3.0 : 7.0的範圍中， 較佳爲2 : 8 (1 : 4)。例如氮氣係被使用作爲惰性氣體。調 整混合氣體之導入速度使得每分鐘以相對於烘烤室1 5全 部體積之1 / 6 0以上與1 / 1 5以下之範圍取代烘烤室1 5中之 混合氣體。烘烤室1 5中之溫度較佳爲1 7 0± 1 0 r的範圍。處 理時間較佳爲8 0 ± 1 0分鐘的範圍。 在以上述條件下使基板進行加熱處理後，停止以加熱 器2 2的加熱。在降低基板溫度至預定溫度（例如，i ） 後，輸送基板P至冷卻室1 7並冷卻至室溫。當基板p被冷 卻時’較佳爲在大氣壓力下將具有-4 0 °C以下之露點的乾燥 混合氣體吹拂至基板P。 藉由烘烤處理，將聚集於基板P與形成於基板P之透 明電極上的濕氣除去’並使透明電極活化。因而，製造具 有優良性能之有機電激發光元件。 200908785 【實例】 使用提供有具有3 0 L全部體積之烘烤室1 5的測試設備 執行預處理（烘烤處理）。烘烤室15中溫度爲170 °C ’且乾 燥時間爲8 0分鐘’並使用氧氣與氮氣體積比例爲1 : 4的 混合氣體。在〇.2至3 .3L/min的範圍中改變被導入於烘烤 室15之混合氣體的流速。評估使用用於執行預處理之基板 P所製造之有機電激發光元件之初始特性、壽命、亮度不 均與暗點之發生的方面。結果示於表1。 ( 藉由應用預定之電壓（例如4.8V)於有機電激發光元 件，以評估初始特性。當得到預定亮度時，則初始特性被 評估爲〇（合格），而當得不到預定亮度時，則初始特性被 評估爲X (失敗）。 藉由施加直流電壓於有機電激發光元件而以固定電流 活化它並測量亮度降低一半之時間長度，以評估其壽命。 當費時5 00小時以上以降低一半亮度時，則壽命被評估爲 〇（合格），當費時5 0 0小時以下以降低一半亮度時，則 I 壽命被評估爲x(失敗）。 藉由在l〇〇°C加熱有機電激發光元件5小時以評估亮 度不均與暗點之發生。當無亮度不均與暗點之發生時，則 亮度不均與暗點發生被評估爲◦(合格），當引起亮度不 均與暗點發生之至少一者，則彼等被評估爲x (失敗）。 當初始特性、壽命、亮度不均與暗點發生之所有方面 均合格時，則有機電激發光元件被評估合格。 -12- 200908785200908785 IX. Description of the Invention: Technical Field of the Invention The present invention relates to a method for pretreating a substrate of an organic electroluminescent device, and more particularly to a substrate for a transparent electrode forming a metal oxide on a substrate. Pretreatment method. Recently, an organic EL element (organic electroluminescent element) of a self-luminous type light-emitting element has been attracting attention. In a basic method for manufacturing an organic electroluminescent device, an anode pattern of a transparent electrode made of IT 0 (indium-tin oxide) is formed on a substrate, and an organic electroluminescent layer and a cathode are laminated on the substrate. on. The organic electroluminescent device is susceptible to the harmful effects of moisture or oxygen. Therefore, if moisture or impurities accumulate on the substrate on which the anode pattern is formed, the fabricated organic electroluminescent element may have a non-luminous region (no light-emitting region) called a dark spot (or dark region), or may have Uneven brightness. Therefore, it is necessary to perform pretreatment of the substrate. [Prior Art] The pretreatment of the substrate includes a treatment for removing moisture causing dark spots from the substrate. A method of pretreating a substrate has been proposed in which moisture is removed by heating and moisture is prevented from re-aggregating on the substrate. For example, Japanese Laid-Open Patent Publication No. 2005-1 9082 2 discloses a moisture removal method for arranging an organic electroluminescent device on a substrate. The organic electroluminescent device has a first electrode, an insulating layer, an organic layer including at least one light-emitting layer, and a second electrode, and are laminated in this order. The method includes the steps of heating the substrate to remove moisture from the substrate at least after forming the insulating layer, and lowering the substrate temperature while maintaining the atmosphere below a low dew point after the moisture removal process. The above publication reveals that the substrate temperature is lowered. 200908785 The gas in the environment is simultaneously released and a new gas having a low dew point is introduced into the environment or a new gas having a low dew point is blown to the substrate. However, the purpose of the pretreatment method disclosed in the above-mentioned publication is limited to the removal of moisture on the substrate. The present inventors have revealed that when the heat treatment for the substrate is performed by introducing only the gaseous nitrogen having a low dew point in the processing chamber, the pretreatment of the transparent electrode forming the metal oxide on the substrate may be deteriorated on the substrate. The performance of the organic electroluminescent device (eg, uneven brightness). Specifically, the inventors have found that the ambient gas used for the heat treatment adversely affects the performance of the transparent electrode made of the metal oxide. It has also been found that the performance of the organic electroluminescent device produced can be deteriorated due to other conditions. SUMMARY OF THE INVENTION An object of the present invention is to provide a substrate pretreatment method in which moisture on a substrate is removed, and when an organic electroluminescence element is manufactured, while being removed by moisture, formation is performed on the substrate. Appropriate surface treatment of the transparent electrode made of metal oxide. In order to achieve the above object, an aspect of the present invention provides a method of pretreating a substrate. A transparent electrode made of a metal oxide is formed on the substrate' and a plurality of layers of the organic electroluminescent device are formed on the transparent electrode after the pretreatment. The pretreatment method includes: accommodating a substrate having a transparent electrode in a processing chamber provided with a heater; heating the substrate while introducing a mixed gas of oxygen and an inert gas into the processing chamber to replace the gas in the processing chamber; The introduction speed of the mixed gas into the processing chamber is such that the mixed gas is introduced into the processing chamber in an amount of 1/60 or more and 1/15 or less of 200,908,785 of the total volume of the processing chamber per minute. Another aspect of the present invention provides a method for fabricating an organic electroluminescent device, comprising: forming a transparent electrode made of a metal oxide on a substrate; and housing the substrate having the transparent electrode in a heating In the processing chamber of the device; heating the substrate while introducing a mixed gas of oxygen and an inert gas into the processing chamber to replace the gas in the processing chamber; setting the introduction speed of the mixed gas into the processing chamber to make the mixed gas in the processing chamber per minute An amount of 1/60 or more and 1/15 or less of the volume is introduced into the processing chamber; the substrate is cooled to room temperature; and a plurality of layers of the organic electroluminescent device are laminated on the transparent electrode. According to the present invention, not only the moisture accumulated on the substrate and the transparent electrode but also the surface reshaping of the transparent electrode made of the metal oxide is simultaneously performed. The "reconstruction of the surface of the transparent electrode" means a process in which the predetermined condition is satisfied by the performance of the organic electroluminescent element manufactured using the substrate on which the surface treatment has been performed. The properties of the organic electroluminescent device include, for example, initial characteristics, lifetime, uneven brightness, and dark spots. Usually, the gas used for the heat drying treatment acts only to transfer the carrier gas which is evaporated to the outside by the heat of the heating. The mixed gas according to the present invention acts as a carrier gas for transporting the evaporated moisture, and also serves to prevent deterioration of the surface condition of the transparent electrode made of the metal oxide due to the removal of moisture. In other words, the oxygen contained in the mixed gas reacts with the metal oxide on the surface of the transparent electrode made of the metal oxide, and the surface condition of the transparent electrode is recombined. Other aspects and advantages of the invention will be apparent from the description and appended claims. The present invention, together with the objects and advantages thereof, is best understood by the following description of the preferred embodiments of the invention. [Embodiment] A specific embodiment of the present invention will be explained with reference to Figs. 1A and 1B. Fig. 1A unintentionally shows the first block forming a plurality of blocks of the organic electroluminescent device manufacturing apparatus. Various different pre-processings are implemented in the first block shown in Figure 1A. The first block has a transfer chamber 11 and a plurality of process chambers 14 to 17 connected to each other via the transfer chamber 11. The first block has a transfer chamber 12 coupled to a second block (not shown) that deposits an organic electroluminescent layer and an electrode. The transport chamber Π has a transport mechanism 13 comprising a robot having a transport arm 8 . The conveying mechanism 13 conveys the substrate to each of the processing chambers 14 to 17 via the conveying chamber 11. The transfer chamber 11, the transfer chamber 12, and each of the processing chambers 14 to 17 are connected to an air extracting device (not shown) for independently evacuating by pumping, and after evacuating by suction It is brought to atmospheric pressure by introduction of an inert gas. The processing chamber includes a reverse chamber 14, a baking chamber 15, a UV processing chamber 16, and a cooling chamber 17, which are connected to the transfer chamber 11 around the transfer chamber 11. In the inversion chamber 14, the substrate on which the transparent electrode pattern is formed on the substrate is reversed. The substrate is transported from the transfer device (not shown) to the inversion chamber 14. The moisture contained in the substrate is removed from the baking chamber 15 and the transparent electrode is recombined. The baking chamber 15 maintains the inside of the baking chamber i 5 in a vacuum state and introduces a pre-200908785 gas into the baking chamber 15. Thus, the baking treatment (heat treatment) of the substrate can be performed in a predetermined environment. UV treatment is performed in the UV treatment chamber 16 to remove organic substances or dust accumulated on the surface of the transparent electrode formed on the substrate. The cooling process for the substrate is performed in the cooling chamber 17. After lowering the temperature of the substrate which has been subjected to the heat treatment in the baking chamber 15 to a predetermined temperature, the substrate is cooled to have a room temperature in a short time by the cooling treatment in the cooling chamber 17. The second block connected to the first block has a mask storage chamber and a plurality of deposition chambers (film forming chambers). The substrate processed in the first block to the second block is transferred via the transfer chamber 12. In each of the deposition chambers of the second block, a plurality of layers of the organic electroluminescent device, such as an organic electroluminescent layer and a cathode layer, are formed on the transparent electrodes on the substrate. As shown in Fig. 1B, a cassette housing chamber 19 is defined in the baking chamber 15, and a substrate cassette 21 is provided in the cassette housing chamber 19. The substrate cassette 2 1 horizontally supports the plurality of substrates P and can be lifted or lowered by the lifting mechanism 20. A sirocco fan 23 is provided in the upper half of the baking chamber 15. The plurality of slits 24a are formed in the partition wall 24 of the cassette housing chamber 19 which is located below the dry heat fan 23. The slit 24a is covered with a HEP A (High Efficiency Particulate Air) filter 25. An air release port 26 is formed in the lower half of the cassette housing chamber 19. A mixed gas supply portion (not shown) provided outside the baking chamber 15 introduces a mixed gas of oxygen and an inert gas through a conduit 27 to an introduction portion formed on a rotating shaft of the dry heat fan 23. The dry heat fan 23 blows the introduced mixed gas to the HEPA filter 25 provided on the partition wall 24. That is, the dry heat fan 23 introduces the mixed gas into the baking chamber 15 at a predetermined introduction speed. The mixed gas blown to the HEPA filter 25 by the dry heat fan 23 passes through the substrate cassette 21' accommodating the plurality of substrates P and the heater 22 provided through the upper half of the baking chamber 15, and by The dry heat fan 23 is again blown to the HEPA filter 25. In other words, the mixed gas blown by the dry heat fan 23 is circulated in the baking chamber 15 at a predetermined flow rate. The flow rate of the mixed gas circulating in the baking chamber 15 is equal to the introduction speed of the mixed gas. The heater 22 is capable of heating the substrate P up to 25 〇 ° C. The dry heat fan 23 is capable of adjusting the introduction speed of the mixed gas into the baking chamber 15 so that the flow rate of the introduced mixed gas is changed in the range of 0 to 550 L/min. A method of manufacturing an organic electroluminescent device (panel) of the manufacturing apparatus constructed as described above will be explained. The substrate 0 in which the IT 0 (indium-tin oxide) pattern was formed as a transparent electrode on the substrate was prepared using a device different from the manufacturing apparatus shown in Figs. 1A and 1B. The substrate P is transferred to the inversion chamber 14 of the manufacturing apparatus by a transfer device (not shown). A film is deposited on the substrate P by deposition upward in each of the deposition chambers of the second block. Therefore, the substrate P is reversed in the inversion chamber 14 so that the surface having the transparent electrode faces downward. Thus, the gripping portion of the transport arm 18 in the transport chamber 挟 can hold the surface of the transparent electrode having the film forming the surface of the substrate P. The substrate is transported from the UV processing chamber 16 to the cooling chamber 17 via the baking chamber 15, and is processed in a state in which the substrate is held by the holding portion of the transport arm 18. Thus, preprocessing is performed. The substrate raft for performing the pretreatment is transported to the first block via the transfer chamber 1 2 by the transport arm 18. In the _• block, each layer forming the organic electroluminescent element is laminated on the substrate ρ. The baking treatment which is one of the pretreatments will be described in detail. -10-200908785 The substrate P inverted in the inversion chamber 14 is subjected to UV treatment in the UV processing chamber 16, and then baked in the baking chamber 15. The plurality of substrates p are simultaneously baked in a state where the substrate P is housed in the substrate cassette 2 1 . In the baking treatment, a mixture gas of oxygen having a dew point of -30 ° C or less at atmospheric pressure and nitrogen having a dew point of -30 ° C or less at atmospheric pressure is introduced from the outside in the baking chamber 1 5 ' by the air release port 2 6 Release part of the mixed gas to the outside. In this state, the heater 22 is heated to a predetermined temperature and the baking treatment is performed at atmospheric pressure for a predetermined time. The introduction speed (flow rate) of the mixed gas is adjusted by the start of the dry heat fan 23. The ratio of oxygen to inert gas (oxygen: inert gas) in the mixed gas to be used is in the range of volume ratio of 1.8: 8.2 to 3.0: 7.0, preferably 2:8 (1:4). For example, nitrogen gas is used as an inert gas. The introduction speed of the mixed gas is adjusted so that the mixed gas in the baking chamber 15 is replaced every minute with respect to the range of 1 / 60 or more and 1 / 15 or less of the total volume of the baking chamber. The temperature in the baking chamber 15 is preferably in the range of 1 70 ± 10 r. The processing time is preferably in the range of 80 ± 10 minutes. After the substrate was subjected to heat treatment under the above conditions, the heating by the heater 22 was stopped. After lowering the substrate temperature to a predetermined temperature (for example, i), the substrate P is transported to the cooling chamber 17 and cooled to room temperature. When the substrate p is cooled, it is preferable to blow a dry mixed gas having a dew point of -40 ° C or lower to the substrate P under atmospheric pressure. The moisture accumulated on the substrate P and the transparent electrode formed on the substrate P is removed by the baking treatment, and the transparent electrode is activated. Thus, an organic electroluminescent device having excellent properties is manufactured. 200908785 [Example] Pretreatment (baking treatment) was performed using a test apparatus provided with a baking chamber 15 having a total volume of 30 L. The temperature in the baking chamber 15 was 170 ° C ' and the drying time was 80 minutes' and a mixed gas having a volume ratio of oxygen to nitrogen of 1: 4 was used. The flow rate of the mixed gas introduced into the baking chamber 15 was changed in the range of 〇. 2 to 3.3 L/min. The aspects of initial characteristics, lifetime, luminance unevenness, and occurrence of dark spots of the organic electroluminescent device manufactured using the substrate P for performing pretreatment were evaluated. The results are shown in Table 1. (Evaluating the initial characteristics by applying a predetermined voltage (for example, 4.8 V) to the organic electroluminescent element. When a predetermined luminance is obtained, the initial characteristic is evaluated as 〇 (pass), and when the predetermined luminance is not obtained, Then the initial characteristic is evaluated as X (failure). By applying a direct current voltage to the organic electroluminescent element to activate it with a fixed current and measuring the length of time by half the brightness, the life is evaluated. When it takes more than 500 hours to reduce At half the brightness, the lifetime is evaluated as 〇 (qualified), and when it takes less than 500 hours to reduce the brightness by half, the I lifetime is evaluated as x (failure). By heating the organic electricity at l ° ° C The light element is evaluated for 5 hours to evaluate the occurrence of uneven brightness and dark spots. When no brightness unevenness and dark spots occur, brightness unevenness and dark spot occurrence are evaluated as ◦ (pass), causing uneven brightness and darkness If at least one of the points occurs, they are evaluated as x (failure). When the initial characteristics, lifetime, brightness unevenness, and all occurrences of dark spots are acceptable, the organic electroluminescent element is evaluated. -12- 200908785
表1 每單位體積流速 (L/min) 初始特性 壽命 亮度不均與暗點發生 評估 0.2 X X X X 0.5 〇 〇 〇 〇 〇 〇 〇 〇 1.0 〇 〇 〇 〇 〇 〇 〇 〇 1.5 〇 〇 〇 〇 〇 〇 〇 〇 2.0 〇 〇 〇 〇 〇 〇 〇 〇 3.3 〇 X X X f ΐ； 根據表1，當混合氣體流速爲〇.2L/min與3.3L/min 時，則有機電激發光元件被評估爲失敗，而當混合氣體流 速在0.5L/min至2.0L/min的範圍中時，有機電激發光元件 則被評估爲合格。具體而言，調整混合氣體之導入速度使 得以每分鐘烘烤室15全部體積之0.5/30( = 1/60)以上及 2.0/3〇(= 1/1 5)以下的量，將混合氣體導入至烘烤室15。使 基板進行加熱處理使得烘烤室1 5中氣體被新導入於烘烤 室1 5之混合氣體取代。因而，得到具有良好性能的有機電 激發光元件。 混合氣體之導入速度（流動速度）愈大、即所導入之混 合氣體的流速愈大，乾燥性能則變得愈佳。然而，在該狀 -1 3 - 200908785 況下，不易發生因混合氣體中的氧所導致之ITO表面重 組，且其劣化有機電激發光元件之性能。若混合氣體之導 入速度（流速），即所導入之混合氣體的流速過小，則基板 不易乾燥且幾乎不發生因氧導致之ΙΤΟ表面重組。 使用提供有具有25 00L全部體積之烘烤室15的有機電 激發光元件製造裝置，在與上述測試設備中得到良好結果 之實例相同的條件下，使基板ρ進行烘烤處理。具體而言， 使基板Ρ進行烘烤處理同時以41.7L/min至166.7L/min之 流速供應混合氣體於烘烤室15。以41.7L/min至166.7L/min 之流速，則以每分鐘烘烤室1 5之全部體積1 /6 0至1 /1 5的 量將混合氣體導入於烘烤室15。使用基板P所製造之有機 電激發光元件具有良好的性能。 可藉由使用氧氣與氬氣混合氣體之電漿處理，執行 ITO表面之重組。然而，由於電漿處理必須在來自濕氣除 去處理之分離處理下執行且需要電漿設備，所以會提高製 造成本。 本具體實施例具有以下優點。 (1)在ITO透明電極形成於基板上之基板P的預處理方 面，使基板P收納於提供有加熱器22之烘烤室1 5中並使 基板P進行加熱處理同時在烘烤室15中導入與釋放氧氣與 惰性氣體之混合氣體，以取代烘烤室1 5中的氣體。設定混 合氣體之導入速度（流速）使得以每分鐘烘烤室1 5全部體積 之1/60以上與1/15以下的量將混合氣體導入於烘烤室15 中。因此，不僅除去聚集於基板P或透明電極上之濕氣’ -14- 200908785 並且重組透明電極之表面。換言之，可對於ιτο透明電極 同時進行2種適當的表面處理。 (2) 在所使用之混合氣體中，氧氣與惰性氣體之比例（氧 氣：惰性氣體）爲體積比1 . 8 : 8.2至3 · 0 : 7.0的範圍中。 因而，確實地對於由ΙΤΟ所製之透明電極表面執行重組處 理。 (3) 藉由執行使用氧氣與惰性氣體混合氣體之預處理 所得的有機電激發光元件，具有與使用具有其表面以電漿 處理進行表面重組之透明電極之基板所製造的有機電激發 光元件相同的性能。因此，比較於使用電漿設備進行電漿 處理之情況，本處理爲簡易且使製造成本降低。 (4) 使用氮氣作爲惰性氣體。因此，比較於使用氬氣或 氯氣作爲惰性氣體的情況，使成本降低。 (5) 在大氣壓力下進行烘烤處理。因此，對於烘烤處理 不需要壓力降低裝置。 (6) 以複數片基板Ρ收納於一個基板卡匣 21中的狀 態，同時使複數片基板Ρ進行烘烤處理。因此，比較於逐 一使基板Ρ進行烘烤處理的情況，提升基板Ρ之烘烤處理 的效率。 本具體實施例雖不受限於此但可如下述修飾。 如第2圖所示’可使用整合地形成烘烤室（加熱室）與 冷卻室之處理室28’作爲用於基板ρ之預處理的處理室。 提供加熱器22於處理室28之下半部且在處理室28中挾持 基板Ρ於加熱器22之上。處理室28係形成於長方形盒中 -15- 200908785 一角落導 當在處理 基板Ρ並 沿著基板 當基板Ρ 導入於處 ΙΤΟ，而 ΙΖΟ(銦鋅 行烘烤處 即在示於 烤處理。 24而乾熱 者其混合 氣體。在 爲氮氣、 ：20.946 : 少量之其 體的混合 並具有一導入開口 29與一空氣釋放口 31，以從 入混合氣體並從該角落之對角的另一角落釋出。 室2 8中進行烘烤處理時，啓動加熱器22以加熱 從導入開口 29導入混合氣體。所導入之混合氣體 P與透明電極30流動，並從空氣釋放口 3〗釋出。 冷卻下來時，停止加熱器2 2的啓動並將浪合氣體 理室2 8。 用於透明電極之材料的金屬氧化物並不限於 可爲用於透明電極之工藝中已知的任何材料，如 氧化物）、ZnO(氧化鋅）、Sn02(氧化錫）或其他。 在示於第2圖之處理室28中使基板P逐一進 理。當未整合地形成烘烤室1 5與冷卻室1 7時， 第1 B圖之烘烤室1 5中，可使基板P逐一進行供 可省略示於第1B圖之烘烤室15中之分隔壁 風扇23可直接吹風至基板卡匣21。 惰性氣體不限於氮氣而可爲氬氣或氦氣或 物。 可使用乾燥空氣作爲氧氣與惰性氣體之混合 該情況下，可進一步降低成本。空氣之主要成分 氧氣與氣氣且氮氣：氧氣：Μ氣之比例爲78.084 0.9 3 0。三種成分之總量爲99.96 %而空氣含有極 他成分。因此，乾燥空氣實質上爲氧氣與惰性氣 氣體。 可使用覆蓋式（sheathed)或紅外線加熱器作爲用於快 200908785 速加熱之加熱器22。 可安置加熱器2 2於烘烤室1 5中之任何位置。 當將氧氣與惰性氣體之混合氣體導入於烘烤室1 5或 處理室2 8中以取代處理室1 5或2 8中之氣體時，氧氣與惰 性氣體不一定必須在將氣體導入於處理室1 5或2 8中之前 混合。例如’可在烘烤室1 5或處理室2 8中分別形成氧氣 導入開口與惰性职(體導入開口，並可在處理室15或28中 混合分別從對應開口所導入之氧氣與惰性氣體。 【圖式簡單說明】 第1 A圖係根據本發明之一具體實施例示意地顯示有 機電激發光元件製造裝置的平面圖。 第1B圖係示意地顯示第ία圖之製造裝置之烘烤室 圖。 第2圖係根據本發明之其他具體實施例示意地顯示處 理室圖。 【主要元件符號說明】 11 輸送室 12 傳遞室 13 輸送機構 14 反轉室 15 烘烤室 16 UV處理室 17 冷卻室 18 輸送手臂 200908785 19 卡匣收納室 20 抬升機構 2 1 基板卡匣 2 2 加熱器 23 乾熱風扇 2 4 分隔壁 24a 狹縫 25 HEPA(高效率微粒子空氣）過濾器 26 空氣釋放口 27 導管 28 處理室 29 導入開口 3 0 透明電極 3 1 空氣釋放口 P 基板 iTable 1 Flow rate per unit volume (L/min) Initial characteristic life Brightness unevenness and dark spot occurrence assessment 0.2 XXXX 0.5 〇〇〇〇〇〇〇〇1.0 〇〇〇〇〇〇〇〇1.5 〇〇〇〇〇〇〇 〇2.0 〇〇〇〇〇〇〇〇3.3 〇XXX f ΐ; According to Table 1, when the mixed gas flow rate is 〇.2L/min and 3.3L/min, the organic electroluminescent element is evaluated as a failure, and when When the mixed gas flow rate was in the range of 0.5 L/min to 2.0 L/min, the organic electroluminescent element was evaluated as acceptable. Specifically, the introduction speed of the mixed gas is adjusted so that the mixed gas is 0.5/30 (= 1/60) or more and 2.0/3 〇 (= 1/1 5) or less of the entire volume of the baking chamber 15 per minute. It is introduced into the baking chamber 15. The substrate is subjected to heat treatment so that the gas in the baking chamber 15 is replaced by the mixed gas newly introduced into the baking chamber 15. Thus, an organic electroluminescent element having good performance is obtained. The larger the introduction speed (flow rate) of the mixed gas, that is, the larger the flow rate of the introduced mixed gas, the better the drying performance. However, in the case of the above -1 3 - 200908785, the ITO surface recombination due to oxygen in the mixed gas is less likely to occur, and it deteriorates the performance of the organic electroluminescent element. If the introduction speed (flow rate) of the mixed gas, that is, the flow rate of the introduced mixed gas is too small, the substrate is not easily dried and the surface recombination due to oxygen hardly occurs. Using the organic electroluminescent device manufacturing apparatus provided with the baking chamber 15 having the entire volume of 25 00 L, the substrate ρ was subjected to baking treatment under the same conditions as those of the above-mentioned test apparatus which gave good results. Specifically, the substrate was subjected to a baking treatment while supplying a mixed gas to the baking chamber 15 at a flow rate of 41.7 L/min to 166.7 L/min. At a flow rate of 41.7 L/min to 166.7 L/min, the mixed gas is introduced into the baking chamber 15 in an amount of 1 / 60 to 1 / 15 of the total volume of the baking chamber per minute. The organic electroluminescent element manufactured using the substrate P has good performance. Recombination of the ITO surface can be performed by plasma treatment using a mixed gas of oxygen and argon. However, since the plasma treatment must be performed under the separation process from the moisture removal treatment and the plasma equipment is required, the manufacturing cost is increased. This embodiment has the following advantages. (1) In the pretreatment of the substrate P on which the ITO transparent electrode is formed on the substrate, the substrate P is housed in the baking chamber 15 provided with the heater 22, and the substrate P is subjected to heat treatment while being in the baking chamber 15 A mixed gas of oxygen and an inert gas is introduced and released to replace the gas in the baking chamber 15. The introduction speed (flow rate) of the mixed gas is set so that the mixed gas is introduced into the baking chamber 15 in an amount of 1/60 or more and 1/15 or less of the total volume of the baking chamber 1 5 per minute. Therefore, not only the moisture "-14-200908785" accumulated on the substrate P or the transparent electrode but also the surface of the reconstituted transparent electrode is removed. In other words, two suitable surface treatments can be simultaneously performed for the ιτο transparent electrode. (2) In the mixed gas used, the ratio of oxygen to inert gas (oxygen: inert gas) is in the range of 1. 8 : 8.2 to 3 · 0 : 7.0. Thus, the recombination treatment is surely performed on the surface of the transparent electrode made of ruthenium. (3) An organic electroluminescent device manufactured by using a substrate pretreated with a mixed gas of oxygen and an inert gas, having an organic electroluminescent device manufactured using a substrate having a transparent electrode whose surface is reorganized by plasma treatment The same performance. Therefore, this processing is simple and the manufacturing cost is lowered as compared with the case of plasma treatment using a plasma equipment. (4) Use nitrogen as the inert gas. Therefore, the cost is lowered as compared with the case where argon gas or chlorine gas is used as the inert gas. (5) Bake at atmospheric pressure. Therefore, a pressure reducing device is not required for the baking process. (6) A plurality of substrates are placed in one substrate cassette 21, and a plurality of substrates are baked. Therefore, the efficiency of the baking treatment of the substrate crucible is improved as compared with the case where the substrate crucible is subjected to the baking treatment one by one. The present embodiment is not limited thereto but may be modified as described below. As shown in Fig. 2, a processing chamber 28' which integrally forms a baking chamber (heating chamber) and a cooling chamber can be used as a processing chamber for pretreatment of the substrate p. A heater 22 is provided in the lower half of the processing chamber 28 and holds the substrate in the processing chamber 28 above the heater 22. The processing chamber 28 is formed in a rectangular box -15-200908785. A corner guide is used to process the substrate Ρ and along the substrate when the substrate Ρ is introduced into the ΙΤΟ, and the 铟 (indium zinc row baking is shown in the baking treatment. 24 The dry heat is a mixture of gas. In the case of nitrogen gas: 20.946: a small amount of the body mixture and has an introduction opening 29 and an air release port 31 to enter the mixed gas and from the other corner of the corner of the corner When the baking treatment is performed in the chamber 28, the heater 22 is started to heat the introduction of the mixed gas from the introduction opening 29. The introduced mixed gas P and the transparent electrode 30 flow and are released from the air discharge port 3. When it comes down, the start of the heater 2 2 is stopped and the gas chamber is closed. The metal oxide used for the material of the transparent electrode is not limited to any material known as a process for a transparent electrode, such as an oxide. ), ZnO (zinc oxide), Sn02 (tin oxide) or others. The substrates P are processed one by one in the processing chamber 28 shown in Fig. 2. When the baking chamber 15 and the cooling chamber 17 are formed unintegrated, in the baking chamber 15 of FIG. 1B, the substrates P can be supplied one by one and can be omitted from the baking chamber 15 shown in FIG. 1B. The partition wall fan 23 can be directly blown to the substrate cassette 21. The inert gas is not limited to nitrogen but may be argon or helium or a gas. Dry air can be used as a mixture of oxygen and inert gas. In this case, the cost can be further reduced. The main components of air Oxygen and gas and nitrogen: Oxygen: Helium ratio is 78.084 0.9 3 0. The total amount of the three components is 99.96% and the air contains the most components. Therefore, the dry air is substantially oxygen and an inert gas. A sheathed or infrared heater can be used as the heater 22 for fast heating at 200908785. The heater 2 2 can be placed anywhere in the baking chamber 15 . When a mixed gas of oxygen and an inert gas is introduced into the baking chamber 15 or the processing chamber 28 to replace the gas in the processing chamber 15 or 28, the oxygen and the inert gas do not necessarily have to be introduced into the processing chamber. Mix before 1 5 or 2 8 . For example, an oxygen introduction opening and an inert introduction opening may be formed in the baking chamber 15 or the processing chamber 28, respectively, and oxygen and an inert gas respectively introduced from the corresponding openings may be mixed in the processing chamber 15 or 28. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A is a plan view schematically showing an apparatus for manufacturing an organic electroluminescence element according to an embodiment of the present invention. Fig. 1B is a view schematically showing a baking chamber of the manufacturing apparatus of Fig. Fig. 2 is a view schematically showing a process chamber according to another embodiment of the present invention. [Description of main components] 11 transfer chamber 12 transfer chamber 13 transport mechanism 14 reverse chamber 15 baking chamber 16 UV processing chamber 17 cooling chamber 18 transport Arm 200908785 19 cassette storage chamber 20 lifting mechanism 2 1 substrate cassette 2 2 heater 23 dry heat fan 2 4 partition wall 24a slit 25 HEPA (high efficiency particulate air) filter 26 air release port 27 conduit 28 processing chamber 29 Inlet opening 3 0 transparent electrode 3 1 air release port P substrate i